((2-Bromo-5-methoxybenzyl)oxy)(tert-butyl)dimethylsilane → 2-[[[(1,1-Dimethylethyl)dimethylsilyl]oxy]methyl]-1-ethenyl-4-methoxybenzene

HRID 392876Notes

Reaction equation

HRID 392876 reaction equation
Br[C:2]1[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][C:3]=1[CH2:4][O:5][Si:6]([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7].[CH2:19](C([Sn])=C(CCCC)CCCC)[CH2:20]CC>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:9]([Si:6]([CH3:8])([CH3:7])[O:5][CH2:4][C:3]1[CH:13]=[C:14]([O:17][CH3:18])[CH:15]=[CH:16][C:2]=1[CH:19]=[CH2:20])([CH3:12])([CH3:11])[CH3:10]

Participants

5

Reactant 2

HCID 22662093((2-Bromo-5-methoxybenzyl)oxy)(tert-butyl)dimethylsilaneHCID 53438229Tri(butyl)vinyltin

Product 1

HCID 226620962-[[[(1,1-Dimethylethyl)dimethylsilyl]oxy]methyl]-1-ethenyl-4-methoxybenzene

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

Under a nitrogen atmosphere, 33.63 9 (0.10 mol) of (2-bromo-5-methoxy-benzyloxy)-tert-butyl-dimethyl-silane (14), 32.18 9 (0.10 mol) of tributylvinyl tin and 4.7 g (0.004 mol) of tetrakis(triphenylphosphine)palladium(0) were combined in 250 mL of toluene, and the solution was heated to reflux for 6 hours. The reaction was allowed to cool to ambient temperature and was quenched with 5% NH4OH (2×100 mL). The organic layer was washed with water (1×200 mL) and brine (1×200 mL), dried over sodium sulfate, filtered and concentrated in vacuo to yield crude product. The crude product was chromatographed on a silica gel column, first with hexane, then with 20% CHCl3 in hexane, and finally with 40% CHCl3 in hexane to afford 25.0 9 (89%) of tert-butyl-dimethyl-(2-vinyl-5-methoxy-benzyloxy)-silane (15).

Workup

  1. temperaturethe solution was heated
  2. temperatureto reflux for 6 hours
  3. customwas quenched with 5% NH4OH (2×100 mL)
  4. washThe organic layer was washed with water (1×200 mL) and brine (1×200 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto yield crude product
  9. customThe crude product was chromatographed on a silica gel column, first with hexane

Sources & evidence

ORD record
ord-9b457cc3636d4c4a960e09ed08057a46
Source dataset
uspto-grants-2004_10
Patent number
US06803470B2

Reaction notes

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